Formation of the double addition products of donor-acceptor cyclopropanes with 2-pyrazolines in the presence of Lewis acids

Article abstract of DOI:10.1007/s11172-012-0266-4

A reaction of excess of cyclopropane-1,1-dicarboxylates substituted at position 2 with 2-pyrazolines in the presence of 3 equiv. of GaCl₃ at 5 C selectively resulted in the cyclopropanes double addition products, viz., N-substituted 1,2-diazabicyclo[3.3.0]octanes. In this case, the first molecule of the starting cyclopropane formed the bicyclic system, whereas the second added at the N-H bond of the adduct formed. When catalytic amount of Sc(OTf)₃ was used in this reaction instead of GaCl₃ at 40 C, besides the corresponding 1,2-diazabicyclo[3.3.0]-octanes, another type of cyclopropane double addition products, viz., N-alkyl-2-pyrazolines, was formed, in which the alkyl chain was assembled from two molecules of the starting cyclopropane. A plausible mechanism for the transformations observed was suggested.

Full text of DOI:10.1007/s11172-012-0266-4

Russian Chemical Bulletin, International Edition, Vol. 61, No. 10, pp. 1917—1924, October, 2012
1917
Formation of the double addition products of donorꢀacceptor cyclopropanes
with 2ꢀpyrazolines in the presence of Lewis acids
R. A. Novikov, Yu. V. Tomilov, and O. M. Nefedov
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 135 6390. Eꢀmail: tom@ioc.ac.ru
A reaction of excess of cyclopropaneꢀ1,1ꢀdicarboxylates substituted at position 2 with 2ꢀpyrꢀ
azolines in the presence of 3 equiv. of GaCl3 at 5 C selectively resulted in the cyclopropanes
double addition products, viz., Nꢀsubstituted 1,2ꢀdiazabicyclo[3.3.0]octanes. In this case, the
first molecule of the starting cyclopropane formed the bicyclic system, whereas the second
added at the N—H bond of the adduct formed. When catalytic amount of Sc(OTf)3 was used in
this reaction instead of GaCl3 at 40 C, besides the corresponding 1,2ꢀdiazabicyclo[3.3.0]ꢀ
octanes, another type of cyclopropane double addition products, viz., Nꢀalkylꢀ2ꢀpyrazolines,
was formed, in which the alkyl chain was assembled from two molecules of the starting cycloꢀ
propane. A plausible mechanism for the transformations observed was suggested.
Key words: donorꢀacceptor cyclopropanes (cyclopropanedicarboxylates), 2ꢀpyrazolines,
catalysis, Lewis acids, double addition.
It is known that cyclopropanes with donor and acꢀ
ceptor substituents in the vicinal position are capable of
the threeꢀmembered ring opening1—5 by thermolysis
or Lewis acid catalysis. A dipolar intermediate formed
as a result of the cleavage of the ꢀ1,2ꢀbond of cycloproꢀ
pane ring can be involved in the formal [2+3]ꢀ or [3+3]ꢀ
cycloaddition reaction with double and triple bonds,
as well as with 1,3ꢀdipoles with the formation of fiveꢀ
or sixꢀmembered rings, including those containing heteroꢀ
atoms.
Recently, we have shown6 that the reaction of substiꢀ
tuted at position 2 cyclopropaneꢀ1,1ꢀdicarboxylates 1 with
1ꢀ and 2ꢀpyrazolines (2 and 3, respectively) was efficiently
catalyzed by Sc and Yb triflates to furnish Nꢀsubstituted
2ꢀpyrazolines 4 and 1,2ꢀdiazabicyclo[3.3.0]octanes 5
(Scheme 1). In this case, the reaction of compounds 1
Scheme 1
R = Ph (a), 2ꢀthienyl (b)
i. R = 2ꢀthienyl (Thi).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1902—1909, October, 2012.
1066ꢀ5285/12/6110ꢀ1917 © 2012 Springer Science+Business Media, Inc.

1918
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Novikov et al.
with 1ꢀpyrazolines 2 at 20 C predominantly gave pyrazolꢀ
ines 4 (yields 61—66%), whereas with 2ꢀpyrazolines 3,
diazabicyclooctanes 5 were predominantly formed (yields
57—61%). The use of anhydrous GaCl3 also promoted the
reaction of cyclopropanedicarboxylates 1 with pyrazolines,
however, in this case the use of the equimolar amount of
GaCl3 with respect to the starting cyclopropane and the
temperature reduced to 0—5 C were required. These conꢀ
ditions gave Nꢀsubstituted 2ꢀpyrazolines 4 as the 1 : 1 adꢀ
ducts with both 1ꢀ and 2ꢀpyrazolines (2 and 3).
However, when the temperature was increased from 5
to 40 C, the reaction of cyclopropaneꢀ1,1ꢀdicarboxylates
1 with pyrazolines 2 and 3 in the presence of GaCl3 led not
only to diazabicyclooctanes 5, but also to 2ꢀpyrazolines 6
and 7 containing an additional alkyl substituent at posiꢀ
tion 3 of the heterocycle,7 with the latter becoming the
major reaction products in excess cyclopropanedicarboxꢀ
ylate (see Scheme 1).
higher 60% (Table 1, entries 3 and 4). However, more
thorough studies of the reaction mixture composition
resulted in the isolation of yet another product, viz.,
Nꢀsubstituted 1,2ꢀdiazabicyclo[3.3.0]octane 8a (Scheme 2),
which was a mixture of four diastereomers (see below).
This compound, like pyrazoline 6a, was a product of the
addition of two molecules of cyclopropane 1a to one molꢀ
ecule of pyrazoline 3a, therefore, it was logically to expect
that an increase in the amount of the donorꢀacceptor
cyclopropane would result in a noticeable increase in the
yield of compound 8a. In fact, when a threeꢀfold excess of
compound 1a was used, the yield of Nꢀsubstituted diazaꢀ
bicyclooctane reached 58% (see Table 1, entry 2), with
some amount of the starting cyclopropane undergoing
polymerization in the course of the reaction.
It was very interesting to observe how the yields of the
product of the double reaction of cyclopropanes 1a,b with
pyrazoline 3a depended on the temperature of the process.
Thus, at 40 C compounds 8a,b were formed in the minor
amounts, whereas their isomers 6a,b were obtained as the
major products (see Table 1, entries 6 and 10). Another
pattern was observed at 5 C: on the contrary, in this case
bicyclic compounds 8a,b noticeably predominated, whereꢀ
as their isomers 6a,b were formed in the minor amounts
(see Table 1, entries 2 and 9). At room temperature, poorꢀ
ly separable mixtures of the corresponding isomeric comꢀ
pounds were obtained in comparable amounts.
In the present work, the studies of the reaction of doꢀ
norꢀacceptor cyclopropanes with 2ꢀpyrazolines were conꢀ
tinued and new directions for these transformations were
found, which led to the formation of the products of double
addition of cyclopropanes to pyrazoline molecule.
Results and Discussion
Earlier,6,7 we have found that the reaction of 2ꢀpyrꢀ
azoline 3a with 2ꢀphenylcyclopropanedicarboxylate 1a
carried out in the presence of the equimolar amount of
GaCl3 at 5 and 20 C led only to compounds 4a, 5a, and
6a (see Scheme 1), the total yield of which was slightly
When 1ꢀpyrazoline 2a was used instead of 2ꢀpyrazolꢀ
ine 3a, no formation of compound 8a was observed under
all the range of conditions applied. No such a product was
obtained in the reaction of Nꢀsubstituted 2ꢀpyrazoline 4a
Scheme 2
Comꢀ
pound
1a
R1
Comꢀ
pound
3a
R2
R3
Comꢀ
pound
5a
5b
5c
R1
R2
R3
Yield
(%)
61
57
82
Comꢀ
pound
8a
8b
8c
R1
R2
R3
Ph
2ꢀThienyl
Me CO2Me
Ph Ph
Ph
2ꢀThienyl Me
Ph Ph
Me
CO2Me
CO2Me
Ph
Ph
2ꢀThienyl
Ph
Me
Me
Ph
CO2Me
CO2Me
Ph
1b
3b
i. GaCl3 (3 equiv.), CH2Cl2, 5 °C, 10 min; ii. Sc(OTf)3 (5 mol.%), CH2Cl2, 20 C, 4 h; iii. GaCl3 (1 equiv.), 5 C, 10 min.

Double addition of DAꢀcyclopropanes to pyrazoline Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1919
with cyclopropane 1a, either. Thus, compounds 8 are the
products of alkylation of the N—H bond in the initially
formed diazabicyclooctanes 5. Though for substituted
cyclopropaneꢀ1,1ꢀdicarboxylates, the cyclopropane ring
opening reaction upon the action of nucleophilic agents
and Lewis acids are studied much poorly than cycloaddiꢀ
tion reactions, nonetheless, there are a number of examꢀ
ples demonstrating the addition of dipolar cyclopropanes
at the N—H bond. Thus, in the presence of Et2AlCl
the donorꢀacceptor cyclopropanes react with ammonia,
primary and secondary amines with the formation of
ꢀaminocarboxylic acid derivatives in from moderate to
high yields.8 Analogous process was also described for the
azoles containing an N—H bond.9 However, because of
lower activity of the latter, the reaction under considerꢀ
ation required more drastic conditions: catalysis with lanꢀ
thanum triflate under microwave irradiation, heating and
increased pressure.
It turned out that an efficient addition of donorꢀacꢀ
ceptor cyclopropanes at the N—H bond can be also proꢀ
moted by gallium trichloride. Earlier,6 such a process has
been already detected in the reaction of cyclopropanes 1
with pyrazoline 3a in the presence of an equimolar amount
of GaCl3 with the formation of pyrazolines 4 (see Scheme 1).
In the present work, it was shown that compounds conꢀ
taining a pyrazolidine fragment in the molecule could be
involved in the analogous reaction. In fact, the reaction of
cyclopropanes 1a,b with diazabicyclooctanes 5a,b in the
presence of GaCl3 led to the formation of compounds 8a,b
in 67—71% yields (see Table 1, entries 7 and 11), in this
case again the best result was obtained when reaction was
carried out at 5 C (entries 7 and 8).
To increase the selectivity of preparation of Nꢀsubstiꢀ
tuted diazabicyclooctanes 8, the process can be divided
into two sequential steps: the first step would include the
synthesis of diazabicyclooctane 5 by the reaction of cycloꢀ
propane 1 with 2ꢀpyrazoline 3a under catalysis with
Sc(OTf)3, in which no formation of cyclopropane double
addition products would occur,6 and then the reaction of
cyclopropanedicarboxylate 1 with the synthesized diazaꢀ
bicyclooctane 5 already in the presence of GaCl3 at 5 C
would be carried out.
In contrast to pyrazoline 3a, a direct reaction of excess
cyclopropanedicarboxylate 1a with 5,5ꢀdiphenylpyrazoꢀ
line 3b in the presence of GaCl3 turned out to be low
efficient (see Table 1, entry 12). The yield of the double
addition product 8c can be increased several times by the
use of the initially obtained diphenyldiazabicyclooctane
5c (see Ref. 6) and by the increase of the reaction time (see
Scheme 2 and Table 1, entry 13). However, because of
considerable steric hindrance created by two phenyl subꢀ
stituents at the NH group, even in this case the conversion
of 5c has proved not high enough, though the starting
cyclopropane was completely spent out.
Substituted diazabicyclooctanes 8a,b are formed as
mixture of four out of eight possible diastereomers in apꢀ
proximately equal proportion. In this case, the isomeric
compositions of the compounds formed in the direct reacꢀ
tion of donorꢀacceptor cyclopropane with pyrazoline and
in its reaction with preliminary obtained diazabicycloꢀ
octane are completely identical. Unlike compounds 8a,b,
diphenylꢀsubstituted diazabicyclooctane 8c was obtained
as a single isomer, that, apparently, can be attributed to
the influence of steric factors.
Table 1. Yields of the reaction products of cyclopropanes 1 with pyrazolines 3 or diazabicyclooctanes 5 in the
a
presence of GaCl3
Entry
Cycloꢀ
propane
Substrate
Molar
ratio
T/C
t/min
Yield (%)
4b
5b
6c
8c
1
2
3
4
5
6
7
8
1a
1a
1a
1a
1a
1a
1a
1a
1b
1b
1b
1a
1a
3a
3a
3a
3a
3a
3a
5a
5a
3a
3a
5b
3b
5c
1.3 : 1
3 : 1
1.3 : 1
3 : 1
1.3 : 1
3 : 1
1.3 : 1
1.3 : 1
3 : 1
5
5
10
10
5
5
5
5
10
5
10
1
10
30
720
20
23
17
19
8
37
5
9
3
7
9
12
36
43
48
78
—
—
13
49
—
—
—
10
58
15
24
6
20
20
40
40
5
20
5
40
5
6
6
8
—
—
25
14
—
2
—
—
10
22
—
8
71
63
50
12
67
9d
32d
9
10
11
12
13
3 : 1
1.3 : 1
3 : 1
5
5
1.3 : 1
—
—
a CH2Cl2, the molar ratio 1 : GaCl3 = 1 : 1.
b A mixture of two diastereomers in the equal ratios.
c A mixture of four diastereomers in the equal ratios.
d Single isomer.

1920
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Novikov et al.
ture to 40 C and the use of a threeꢀfold excess of the
starting cyclopropane partially changed the course of the
reaction. In this case, the yield of diazabicyclooctane 5a
remained virtually the same, but a longꢀchain Nꢀalkylꢀ
pyrazoline 9 was formed as the double addition product of
cyclopropane 1a to pyrazoline 3a instead of most part of
compound 4a (Scheme 3).
This compound, like other double addition products 6
and 8, was formed as a mixture of four stereoisomers in
approximately equal ratio. The structure and the isomeric
composition of compound 9 were established using homoꢀ
and heteronuclear 1D and 2D NMR correlation spectra
DEPT, COSY, TOCSY, NOESY, HSQC and HMBC.
8: R1 = CH=CH (a), S (b); R2 = Me, R3 = CO2Me (a, b);
1 = CH=CH, R2 = R3 = Ph (c)
R
1
For the H and 13C NMR spectra of all the isomers, the
Fig. 1. Some characteristic crossꢀpeaks in the 2D 1H NOESY
NMR spectra of compounds 8a—c.
signals for the HC=N fragment found in the downfield
regions of the spectra (H 6.5—6.6 and C 136—137) are
characteristic, where signals for the isomeric compounds 6
and 8 are absent. We also found relative configurations of
substituents at atoms C(5) and C(1´)6, however, stereoꢀ
chemistry of these centers was not unambiguously related
to the configuration of atoms C(1´) and C(4´).
The structures and the isomeric composition of comꢀ
pounds 8a—c were established using homoꢀ and heteroꢀ
nuclear 1D and 2D NMR correlation spectra DEPT,
COSY, TOCSY, NOESY, HSQC, and HMBC. The arꢀ
rows in Fig. 1 show some characteristic crossꢀpeaks in the
2D 1H NOESY NMR spectra of compounds 8a—c,
demonstrating retention of stereochemistry of the 8ꢀphenꢀ
ylꢀ1,2ꢀdiazabicyclo[3.3.0]octane fragment for all the diꢀ
astereomers with respect to the starting compounds 5a—c
(see Ref. 6). In addition, we also found relative configuraꢀ
tion of substituents at atoms C(3) and C(1´) for a number
of examples, however, the stereochemistry of these cenꢀ
ters was not unambiguously related to the configuration of
atoms C(5) and C(8).
In the present work, we also obtained the third type of
the double addition products of cyclopropane to pyrazoꢀ
lines. Thus, the reaction of equimolar amounts of pyrazoꢀ
line 3a and cyclopropanedicarboxylate 1a catalyzed with
Sc(OTf)3 at room temperature resulted in the isolation of
diazabicyclooctane 5a and Nꢀsubstituted pyrazoline 4a as
the only products.6 However, an increase in the temperaꢀ
It could have been expected that compound 9 resulted
from the further reaction of pyrazoline 4a with the interꢀ
mediate formed upon the opening of cyclopropane 1a by
the action of Lewis acid. However, such a suggestion had
proved wrong, since an independent experiment showed
that such a reaction did not take place under the same
conditions. It is also difficult to picture this reaction as
proceeding through the formation of the intermediate reꢀ
sulted from the initial reaction of two molecules of the
donorꢀacceptor cyclopropane, since in the presence of
Sc(OTf)3 at 40 C these cyclopropanes themselves gave no
any dimeric products. Taking into account these observaꢀ
tion, it can be suggested that the intermediate I can iniꢀ
tially attack both nitrogen atoms of the starting 2ꢀpyrazolꢀ
ine. Subsequent cyclization occurs upon attack at atom
N(2), leading to diazabicyclooctanes.6 The alkylation at
atom N(1) leads to the intermediate II, which either irreꢀ
versibly converts to pyrazoline 4 or, because of the presꢀ
Scheme 3
i. 40 C, 12 h, CH2Cl2.

Double addition of DAꢀcyclopropanes to pyrazoline Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1921
Scheme 4
ence of excess of donorꢀacceptor cyclopropane, adds a
second molecule of 1, that leads to the intermediate III
and then to pyrazoline 9 (Scheme 4).
Experimental
H and 13C NMR spectra were recorded on a Bruker AMXꢀ400
1
spectrometer (400.1 and 100.6 MHz, respectively) for solutions
in CDCl3 containing 0.05% Me4Si as an internal standard. Asꢀ
signment of the signals and determination of the isomeric comꢀ
position of compounds formed were performed using homoꢀ and
heteronuclear 1D and 2D correlation spectra DEPT, COSY,
TOCSY, NOESY, XHCORR, HSQC, and HMBC. High resoꢀ
lution mass spectra (ESIꢀHRMS) were obtained on a micrOTOF
instrument. Thinꢀlayer chromatography was carried out on Silufol
chromatographic plates (Merck). Silica gel 60 (0.040—0.063 mm,
Merck) was used for preparative chromatography. Cyclopropanes
1a,b were obtained by the Corey—Chaikovskii reaction.10,11
Pyrazolines 3a,b were synthesized according to the described
procedures.12,13 Diazabicyclooctanes 5a—c were obtained by the
formal [2+3] cycloaddition reaction of donorꢀacceptor cycloꢀ
propanes 1a,b to pyrazolines 2a,b using procedures developed by
us earlier.6 The Lewis acids Sc(OTf)3 (Acros Organics) and
GaCl3 (Aldrich) were used in the work. All the manipulations
with GaCl3 were carried out under dry argon. Solvents of the
reagent grade. (>99.5%) were used without additional purificaꢀ
tion. Dichloromethane was first stored over granulated KOH
and then distilled over P2O5 under dry argon.
Theoretically, the intermediate III, similarly to the
intermediate II, could have add another molecule of the
donorꢀacceptor cyclopropane, however, no such products
were observed in the reaction mixture. It should be noted
that no examples of the formation of such products
of addition to the substrate of two molecule of the donorꢀ
acceptor cyclopropane, directly bonded to each other,
were described earlier. Therefore, the preparation of comꢀ
pound 9 is a new type of the reaction of the donorꢀacꢀ
ceptor cyclopropane 1a. Note that similar cycloproꢀ
pane 1b, containing a thienyl substituent, does not give
such a reaction.
In conclusion, in addition to the recently described
method for the introduction of two donorꢀacceptor cycloꢀ
propane fragments at positions 1 and 3 of pyrazolines,7
we found yet two more types of the reaction of the doꢀ
norꢀacceptor cyclopropanes with 2ꢀpyrazolines in the
presence of Lewis acids, which were accompanied by the
formation of cyclopropane double addition products, viz.,
Nꢀsubstituted 1,2ꢀdiazabicyclo[3.3.0]octanes and Nꢀalkylꢀ
2ꢀpyrazolines, in which the alkyl chain was formed of
two molecules of the starting cyclopropane. The use
of different Lewis acids and varying the temperature
allowed us to selectively obtain products with the different
type of the double addition of cyclopropanes to 2ꢀpyrꢀ
azolines.
Reaction of dimethyl 2ꢀarylcyclopropaneꢀ1,1ꢀdicarboxylates
(1) with 2ꢀpyrazolines 3 and diazabicyclooctanes 5 in the presence
of GaCl3 (general procedure). Solid GaCl3 (0.65 or 1.5 mmol)
was added in one portion to a solution of cyclopropane 1a,b
(0.65 or 1.5 mmol (see Table 1)) and pyrazoline 3a,b (0.5 mmol)
or diazabicyclooctane 5a—c (0.5 mmol) in anhydrous dichloroꢀ
methane (3—5 mL) under argon at a required temperature and
with vigorous stirring, then the stirring was continued during the

1922
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Novikov et al.
time indicated in Table 1. After that, the reaction mixture was
diluted with 5% aqueous HCl at 0 C to pH 3 and extracted with
dichloromethane (3×10 mL). The organic layers were combined,
dried with anhydrous MgSO4 and the solvent was evaporated
in vacuo. The residue was separated by column chromatography
on silica gel (eluent benzene—AcOEt), isolating compounds 4—8.
If necessary, the products additionally were purified using TLC
on silica gel.
3.16 (dd, 1 H, Hb(7), 2J = 14.5 Hz, 3J = 9.5 Hz); 3.48, 3.63, 3.68,
3.71, 3.78 (all s, 3 H each, 5 OMe); 3.72 (m, 1 H, H(1´)); 3.85
(dd, 1 H, H(5), 3J = 11.3 Hz, 3J = 6.4 Hz); 4.23 (dd, 1 H, H(8),
3J = 9.5 Hz, 3J = 8.2 Hz); 7.17—7.48 (m, 8 H, 2 Ho, 4 Hm, 2 Hp,
2 Ph); 7.62 (m, 2 H, Ho, Ph at C(8)). 13C NMR (CDCl3), : 23.6
(Me); 36.6 (C(2´)); 38.8 (C(7)); 41.7 (C(4)); 48.7 (C(3´)); 52.1,
52.3, 52.5, 52.9, 53.1 (5 OMe); 59.3 (C(6)); 60.5 (C(1´)); 67.1
(C(5)); 69.4 (C(8)); 71.6 (C(3)); 127.1, 127.3 (Cp, 2 Ph); 128.1,
128.2, 128.6, 129.3 (Co, Cm, 2 Ph); 142.9 (Cipso, 2 Ph); 169.1
(COO at C(3´)); 170.0, 170.1 (COO, the ratio 3 : 1).
(5R*,8S*)ꢀTrimethyl 2ꢀ[3,3ꢀbis(methoxycarbonyl)ꢀ1ꢀphenylꢀ
propꢀ1ꢀyl]ꢀ3ꢀmethylꢀ8ꢀphenylꢀ1,2ꢀdiazabicyclo[3.3.0]octaneꢀ
3,6,6ꢀtricarboxylate (8a). A. The residue left after the carrying
out the reaction of cyclopropane 1a (0.35 g, 1.5 mmol) and
2ꢀpyrazoline 3a (71 mg, 0.5 mmol) in the presence of GaCl3
(0.26 g, 1.5 mmol) (see Table 1, entry 2) was separated by colꢀ
umn chromatography on silica gel (eluent benzene—AcOEt, graꢀ
dient from 20 : 1 to 5 : 1) to obtain pyrazoline 4a (43 mg, 23%),
diazabicyclooctane 5a (9 mg, ~5%), substituted pyrazoline 6a
(36 mg, 12%), and substituted diazabicyclooctanes (5R*,8S*)ꢀ8a
(four diastereomers 8aa—8ad approximately in the equal ratio,
totaling 0.18 g, 58%), of which three diastereomers were sucꢀ
cessfully isolated in the individual state, whereas the fourth only
as a predominant isomer. In this case, all the diastereomers were
characterized by the same relative configuration of substituents
at atoms C(5) and C(8), however, we failed to unambiguously
correlate stereochemistry of these centers with positions of subꢀ
stituents at atoms C(3) and C(1´). Compounds 4a—6a and their
isomeric composition were identical to those for the samples
obtained earlier.5,6
Compound 8ac. Colorless dense oil. HRMS (ESI): [M + К]+,
calculated for C32H38N2O10K 649.2158, found 649.2153.
1H NMR (CDCl3), : 1.05 (ddd, 1 H, Ha(2´), 2J = 14.3 Hz,
3J = 7.7 Hz, 3J = 6.7 Hz); 1.33 (s, 3 H, Me); 1.89 (dd, 1 H,
Ha(4), 2J = 11.9 Hz, 3J = 5.6 Hz); 1.92 (ddd, 1 H, Hb(2´),
3
3
2J = 14.3 Hz, J = 7.7 Hz, J = 6.7 Hz); 2.38 (dd, 1 H, Ha(7),
3
2
2J = 14.2 Hz, J = 9.4 Hz); 2.72 (dd, 1 H, Hb(4), J = 11.9 Hz,
3J = 12.3 Hz); 3.19 (dd, 1 H, Hb(7), 2J = 14.2 Hz, 3J = 8.7 Hz);
3.42 (s, 3 H, CO2Me at C(3)); 3.43 (t, 1 H, H(3´), 3J = 7.7 Hz);
3.60, 3.71 (both s, 3 H each, CO2Me at C(3´)); 3.74, 3.88 (both s,
3 H each, CO2Me at C(6)); 3.85 (t, 1 H, H(1´), 3J = 6.7 Hz);
4.42 (dd, 1 H, H(5), 3J = 12.3 Hz, 3J = 5.6 Hz); 4.62 (dd, 1 H,
H(8), 3J = 9.4 Hz, 3J = 8.7 Hz); 7.01 (m, 2 H, Ho, Ph at C(1´));
7.09 (m, 1 H, Hp, Ph at C(1´)); 7.13 (m, 2 H, Hm, Ph at C(1´));
7.24 (m, 1 H, Hp, Ph at C(8)); 7.31 (m, 2 H, Hm, Ph at C(8));
7.42 (m, 2 H, Ho, Ph at C(8)). 13C NMR (CDCl3), : 21.4 (Me);
36.9 (C(2´)); 37.4 (C(7)); 44.5 (C(4)); 50.0 (C(3´)); 52.1 (CO2Me
at C(3)); 52.25, 52.27 (CO2Me at C(3´)); 53.0, 53.3 (CO2Me at
C(6)); 59.0 (C(6)); 61.5 (C(1´)); 66.7 (C(5)); 69.1 (C(8)); 71.2
(C(3)); 127.0 (Cp, Ph at C(1´)); 127.7 (Cp, Ph at C(8)); 128.02
(Co, Ph at C(1´)); 128.06 (Cm, Ph at C(1´)); 128.2 (Co, Ph at
C(8)); 129.5 (Cm, Ph at C(8)); 141.2 (Cipso, Ph at C(8)); 143.5
(Cipso, Ph at C(1´)); 169.7, 170.2 (2 COO at C(3´)); 170.0, 171.5
(2 COO at C(6));176.5 (COO at C(3)).
B. The residue left after the carrying out the reaction of cycloꢀ
propane 1a (152 mg, 0.65 mmol) and diazabicyclooctane 5a (0.19 g,
0.5 mmol, a mixture of diastereomers (1 : 1)) in the presence of
GaCl3 (114 mg, 0.65 mmol) (see Table 1, entry 7) was separated
by column chromatography to obtained compound 8a (totaling
0.22 g, 71%) with the same ratio of diastereomers as in entry A.
Compound 8aa. Colorless dense oil. HRMS (ESI): [M + К]+,
calculated for C32H38N2O10K 649.2158, found 649.2152.
1H NMR (CDCl3), : 1.55 (m, 2 H, C(2´)H2); 1.60 (s, 3 H, Me);
2.00 (dd, 1 H, Ha(4), 2J = 12.4 Hz, 3J = 12.0 Hz); 2.18 (dd, 1 H,
Ha(7), 2J= 14.5 Hz, 3J = 7.2 Hz); 2.33 (dd, 1 H, Hb(4), 2J = 12.4 Hz,
3J = 5.4 Hz); 3.10 (dd, 1 H, H(3´), 3J = 8.1 Hz, 3J = 7.6 Hz);
3.10 (s, 3 H, OMe at C(3)); 3.33 (dd, 1 H, Hb(7), 2J = 14.5 Hz,
3J = 10.0 Hz); 3.49, 3.65 (both s, 3 H each, 2 OMe at C(3´));
3.60 (dd, 1 H, H(1´), 3J = 8.8 Hz, 3J = 8.8 Hz, 3J = 7.4 Hz);
3.71, 3.80 (both s, 3 H each, 2 OMe at C(6)); 4.18 (dd, 1 H,
H(8), 3J = 10.0 Hz, 3J = 7.2 Hz); 4.47 (dd, 1 H, H(5), 3J = 12.0 Hz,
3J = 5.4 Hz); 7.19 (m, 2 H, Hp, 2 Ph); 7.28 (m, 4 H, Hm, 2 Ph);
7.36 (m, 2 H, Ho, Ph at C(8)); 7.56 (m, 2 H, Ho, Ph at C(1´)).
13C NMR (CDCl3), : 28.6 (Me); 37.5 (C(2´)); 39.4 (C(7)); 41.5
(C(4)); 49.0 (C(3´)); 51.6 (CO2Me at C(3)); 52.2, 52.3 (2 CO2Me at
C(3´)); 52.99, 53.04 (2 CO2Me at C(6)); 59.5 (C(6)); 60.5 (C(1´));
69.7 (C(5)); 71.0 (C(3)); 72.7 (C(8)); 127.0 (Cp, Ph at C(1´));
127.2 (Cp, Ph at C(8)); 127.9 (Cm, Ph at C(1´)); 128.0 (Co, Ph at
C(8)); 128.6 (Cm, Ph at C(8)); 129.1 (Co, Ph at C(1´)); 141.6
(Cipso, Ph at C(1´)); 143.5 (Cipso, Ph at C(8)); 168.9, 169.87 (2 COO
at C(3´)); 169.91, 171.5 (2 COO at C(6)); 173.4 (COO at C(3)).
Compound 8ab. Colorless dense oil. HRMS (ESI): [M + H]+,
calculated for C32H39N2O10 611.2599, found 611.2593. 1H NMR
(CDCl3), : 1.32 (s, 3 H, Me); 1.58 (m, 2 H, CH2(2´)); 1.75 (dd,
1 H, Ha(4), 2J = 12.6 Hz, 3J = 6.4 Hz); 2.23 (dd, 1 H, Ha(7),
(5R*,8S*)ꢀTrimethyl 2ꢀ[3,3ꢀbis(methoxycarbonyl)ꢀ1ꢀ(2ꢀ
thienyl)propꢀ1ꢀyl]ꢀ3ꢀmethylꢀ8ꢀ(2ꢀthienyl)ꢀ1,2ꢀdiazabicycloꢀ
[3.3.0]octaneꢀ3,6,6ꢀtricarboxylate (8b). A. The residue left after
the carrying out the reaction of cyclopropane 1b (0.36 g,
1.5 mmol) and 2ꢀpyrazoline 3a (71 mg, 0.5 mmol) in the presꢀ
ence of GaCl3 (0.26 g, 1.5 mmol) (see Table 1, entry 9) was
separated by column chromatography on silica gel (eluent benꢀ
zene—AcOEt (10 : 1)) to obtain pyrazoline 4b (48 mg, 25%),
diazabicyclooctane 5b (19 mg, 10%), substituted pyrazoline 6b
(40 mg, 13%), and substituted diazabicyclooctanes 8b (totaling
155 mg, 50%) (a mixture of four diastereomers in the equal
ratios). Compounds 4b—6b and their isomeric composition were
identical to those for the samples obtained earlier.5,6
B. The residue left after the carrying out the reaction of
cyclopropane 1b (156 mg, 0.65 mmol) and diazabicyclooctane
5b (0.19 g, 0.5 mmol, a mixture of diastereomers (1 : 1)) in the
presence of GaCl3 (114 mg, 0.65 mmol) (see Table 1, entry 11)
was separated by column chromatography on silica gel to obtain
compound 8b (208 mg, 67%) (a mixture of four diastereomers in
the equal ratios).
Compound 8b (a mixture of four diastereomers). Colorꢀ
less dense oil. HRMS (ESI): [M + Na]+, calculated for
C28H34N2O10S2Na 645.1547, found 645.1543. 1H NMR (CDCl3),
: 0.85, 0.88, 1.48, 1.56 (all s, 3 H*, 4 Me); 1.85 (dd, 1 H, H(4) in
2
2J = 14.5 Hz, 3J = 8.2 Hz); 2.79 (dd, 1 H, Hb(4), J = 12.6 Hz,
* The integral intensities of the signal are given as calculated
based on the intensities of a single proton of one isomer.
3
3J = 11.3 Hz); 3.10 (dd, 1 H, H(3´), J = 9.2 Hz, 3J = 6.2 Hz);

Double addition of DAꢀcyclopropanes to pyrazoline Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
1923
isomer 1, J = 12.6 Hz, J = 6.4 Hz); 1.91 (dd, 1 H, H(4) in isomer 2,
J = 12.3 Hz, J = 12.2 Hz); 2.89 (dd, 1 H, H(4) in isomer 3,
J = 15.0 Hz, J = 7.9 Hz); 2.95 (dd, 1 H, H(4) in isomer 4,
J = 13.0 Hz, J = 10.1 Hz); 1.53—1.73 (m, 8 H, 4 C(2´)H2);
4.13—4.35 (m, 6 H, 4 H(1´), 2 H(5)); 3.97—4.08 (m, 2 H, 2 H(5)
or 2 H(8)); 4.53 (dd, 1 H, H(5) or H(8), J = 9.7 Hz, J = 6.6 Hz);
4.55—4.62 (m, 2 H, 2 H(5) or 2 H(8)); 4.65 (dd, 1 H, H(5) or
H(8), J = 12.1 Hz, J = 5.5 Hz); 3.07—3.23 (m, 3 H, 3 H(7));
3.23—3.37 (m, 5 H, 4 H(3´), H(7)); 2.26—2.84 (m, 8 H, 4 H(4),
4 H(7)); 3.10, 3.26, 3.40, 3.54, 3.57, 3.59, 3.659, 3.664, 3.70,
3.711, 3.716, 3.720, 3.75, 3.76, 3.77, 3.78, 3.79, 3.80, 3.81, 3.82
(all s, 3 H each, 5 CO2Me in isomers 1—4); 6.58—7.07 (m, 16 H,
H(3), H(4), 2 thienyl); 7.11—7.25 (m, 8 H, H(5)).
(5R*,8S*)ꢀDimethyl 2ꢀ[3,3ꢀbis(methoxycarbonyl)ꢀ1ꢀphenylꢀ
propꢀ1ꢀyl]ꢀ3,3,8ꢀtriphenylꢀ1,2ꢀdiazabicyclo[3.3.0]octaneꢀ6,6ꢀ
dicarboxylate (8c). A. The residue left after the carrying out the
reaction of cyclopropane 1a (0.35 g, 1.5 mmol) and 2ꢀpyrazoꢀ
line 3b (0.11 g, 0.5 mmol) in the presence of GaCl3 (264 mg,
1.5 mmol) (see Table 1, entry 12) was separated by column
chromatography on silica gel (eluent benzene—AcOEt, gradient
from 20 : 1 to 5 : 1) to obtain pyrazoline 4c (5 mg, 2%), diazabiꢀ
cyclooctane 5c (18 mg, 8%), and substituted diazabicycloꢀ
octane 8c (31 mg, 9%) as a single isomer. Compounds 4c and 5c
are identical to the samples obtained earlier.5,6
92 mg, 30%) (a mixture of four diastereomers approximately in
the equal ratios), of which two (9c,d) were obtained in the indiꢀ
vidual state, whereas another two (9a,b), as a mixture with each
other. A mixture of isomers 9a,b. Colorless dense oil. HRMS
(ESI): [M + Na]+, calculated for C32H38N2O10Na 633.2419,
found 633.2410; [M + K]+, calculated for C32H38N2O10
649.2158, found 649.2161.
K
Isomer (5R*,1´R*)ꢀ9a. 1H NMR (CDCl3), : 0.82 (s, 3 H,
Me); 1.99 (dd, 1 H, Ha(2´); 2J = 14.4 Hz, 3J = 3.3 Hz); 2.26
(ddd, 1 H, Ha(5´), 2J = 13.0 Hz, 3J = 9.8 Hz, 3J = 5.6 Hz); 2.37
(dd, 1 H, Ha(4), 2J = 17.3 Hz, 3J = 1.9 Hz); 2.69 (ddd, 1 H,
2
Hb(5´), J = 13.0 Hz, 3J = 9.5 Hz, 3J = 3.2 Hz); 2.76 (dd, 1 H,
Hb(4), 2J = 17.3 Hz, 3J = 2.4 Hz); 2.95 (dd, 1 H, Hb(2´),
3
3
2J = 14.4 Hz, J = 9.9 Hz); 3.07 (dd, 1 H, H(6´), J = 9.5 Hz,
3J = 5.6 Hz); 3.42 (dd, 1 H, H(4´), 3J = 9.8 Hz, J = 3.2 Hz);
3
3.45, 3.47, 3.70, 3.78, 3.88 (all s, 3 H each, 5 OMe); 4.69 (dd, 1 H,
H(1´), 3J = 9.9 Hz, 3J = 3.3 Hz); 6.49 (dd, 1 H, H(3), 3J = 2.4 Hz,
3J = 1.9 Hz); 7.00—7.38 (m, 10 H, 2 Ph).
Isomer (5S*,1´R*)ꢀ9b. 1H NMR (CDCl3), : 1.56 (s, 3 H,
Me); 2.07 (dd, 1 H, Ha(2´), 2J = 14.6 Hz, 3J = 4.4 Hz); 2.24
(ddd, 1 H, Ha(5´), 2J = 13.2 Hz, 3J = 11.9 Hz, 3J = 4.0 Hz); 2.57
(dd, 1 H, Ha(4), 2J = 17.7 Hz, 3J = 1.1 Hz); 2.73 (ddd, 1 H,
3
Hb(5´), 2J = 13.2 Hz, 3J = 9.8 Hz, J = 1.4 Hz); 2.78 (s, 3 H,
CO2Me at C(5)); 2.93 (dd, 1 H, Hb(2´); 2J = 14.6 Hz, 3J = 9.4 Hz);
3
3
B. The residue left after the carrying out the reaction of
cyclopropane 1a (76 mg, 0.32 mmol) and diazabicyclooctane 5c
(114 mg, 0.25 mmol) in the presence of GaCl3 (57 mg, 0.32 mmol)
(see Table 1, entry 13) was separated by column chromatography
on silica gel (eluent benzene—AcOEt (10 : 1)) to obtain comꢀ
pound 8c (55 mg, 32%) as colorless dense oil. HRMS (ESI):
[M + H]+, calculated for C41H43N2O8 691.3014, found 691.3007.
1H NMR (CDCl3), : 1.88 (ddd, 1 H, Ha(2´), 2J = 14.2 Hz,
3.05 (dd, 1 H, H(6´), J = 9.8 Hz, J = 4.0 Hz); 3.14 (dd, 1 H,
Hb(4), 2J = 17.7 Hz, 3J = 1.3 Hz); 3.49 (dd, 1 H, H(4´),
3J = 11.9 Hz, 3J = 1.4 Hz); 3.48, 3.53, 3.73, 3.78 (all s, 3 H each,
3
4 OMe); 4.32 (dd, 1 H, H(1´), 3J = 9.4 Hz, J = 4.4 Hz); 6.49
(dd, 1 H, H(3), 3J = 1.3 Hz, 3J = 1.1 Hz); 7.02 (m, 2 H, Ho,
Ph at C(4´)); 7.10 (m, 2 H, Hm, Ph at C(4´)); 7.13 (m, 1 H, Hp,
Ph at C(4´)); 7.16 (m, 1 H, Hp, Ph at C(1´)); 7.20 (m, 2 H, Hm,
Ph at C(1´)); 7.31 (m, 2 H, Ho, Ph at C(1´)). 13C NMR (CDCl3),
: 21.3 (Me); 31.5 (C(5´)); 41.0 (C(2´)); 47.0 (C(4)); 50.0 (C(4´));
50.6 (C(6´)); 51.2 (CO2Me at C(5)); 51.8, 51.9, 52.4, 52.5
(4 OMe); 57.0 (C(1´)); 61.1 (C(3´)); 67.7 (C(5)); 126.8 (br),
126.9 (2 Cp); 128.2, 128.3, 128.7 (2 Cm, Co); 129.5 (br, Co, Ph at
3
2
3J = 8.9 Hz, J = 5.8 Hz); 2.22 (dd, 1 H, Ha(7), J = 14.4 Hz,
3J = 9.1 Hz); 2.67 (ddd, 1 H, Hb(2´), 2J = 14.2 Hz, 3J = 8.8 Hz,
3J = 5.3 Hz); 2.70 (dd, 1 H, Ha(4), 2J = 13.3 Hz, 3J = 12.3 Hz);
3
3
3.06 (dd, 1 H, H(3´), J = 8.9 Hz, J = 5.3 Hz); 3.28 (dd, 1 H,
Hb(4), 2J = 13.3 Hz, 3J = 6.6 Hz); 3.07 (dd, 1 H, Hb(7), 2J = 14.4
Hz, 3J = 8.9 Hz); 3.37 (dd, 1 H, H(1´), 3J = 8.8 Hz, 3J = 5.8 Hz);
3.57, 3.63, 3.78, 3.92 (all s, 3 H each, 4 OMe); 3.99 (dd, 1 H,
H(8), 3J = 9.1 Hz, 3J = 8.9 Hz); 4.81 (dd, 1 H, H(5), 3J = 12.3 Hz,
3J = 6.6 Hz); 6.05 (m, 2 H, Ho, 1 Ph); 6.78 (m, 2 H, Hm, 1 Ph);
6.88 (m, 1 H, Hp, 1 Ph); 7.11—7.44 (m, 15 H, 3 Ph). 13C NMR
(CDCl3), : 35.3 (C(2´)); 39.3 (C(7)); 49.8 (C(3´)); 51.2 (C(4));
52.3, 53.0, 53.3 (4 OMe, the ratio 2 : 1 : 1); 59.6 (C(6)); 63.0
(C(1´)); 67.0 (C(8)); 69.8 (C(5)); 73.5 (C(3)); 125.5, 126.2, 126.3,
127.2 (Co in all the Ph); 127.3, 127.4, 127.5, 128.2, 128.3 (3 C),
129.4 (Cm and Cp in all the Ph); 142.5, 143.3, 144.8, 151.5
(Cipso in all the Ph); 169.9, 170.1, 170.3, 171.8 (4 COO).
C(4´)); 136.6 (C(3)); 138.4 (Cipso, Ph at C(4´)); 145.1 (Cipso
,
Ph at C(1´)); 169.3, 169.4, 169.5, 170.8 (4 COO); 172.3 (COO
at C(5)).
Isomer (5S*,1´R*)ꢀ9c. Colorless dense oil. HRMS (ESI):
[M + Na]+, calculated for C32H38N2O10Na 633.2419, found
633.2411; [M + K]+, calculated for C32H38N2O10K 649.2158,
1
found 649.2164. H NMR (CDCl3), : 1.46 (s, 3 H, Me); 2.04
(dd, 1 H, Ha(2´), 2J = 14.7 Hz, 3J = 3.1 Hz); 2.43 (ddd, 1 H,
Ha(5´), 2J = 13.6 Hz, 3J = 11.1 Hz, 3J = 2.5 Hz); 2.56 (dd, 1 H,
Ha(4), 2J = 17.0 Hz, 3J = 1.4 Hz); 2.56 (ddd, 1 H, Ha(5´),
2J = 13.6 Hz, 3J = 12.1 Hz, 3J = 4.2 Hz); 2.72 (s, 3 H, CO2Me at
3
C(5)); 2.89 (dd, 1 H, Hb(2´), 2J = 14.7 Hz, J = 9.8 Hz); 2.93
Methyl 1ꢀ[3,3,6,6ꢀtetra(methoxycarbonyl)ꢀ1,4ꢀdiphenylhexꢀ
1ꢀyl]ꢀ5ꢀmethylꢀ4,5ꢀdihydroꢀ1Hꢀpyrazolꢀ5ꢀcarboxylate (9). The
compound Sc(OTf)3 (63 mg, 0.15 mmol) was added in one porꢀ
tion to a solution of cyclopropane 1a (351 mg, 1.5 mmol) and
pyrazoline 3a (71 mg, 0.5 mmol) in anhydrous dichloromethane
(5 mL) under argon and the reaction mixture was stirred for 12 h
at 40 C. Then, a 5% aq. HCl was added to pH 3 at 0 C and
extracted with CH2Cl2 (3×10 mL). The organic layers were comꢀ
bined, dried with anhydrous MgSO4, and the solvent was evapoꢀ
rated in vacuo. The residue was separated by column chromatogꢀ
raphy on silica gel (eluent benzene—AcOEt, gradient from 20 : 1
to 5 : 1) to obtain pyrazoline 4a (9 mg, 5%), diazabicyclooctane
5a (117 mg, 62%), and substituted pyrazolines 9a—d (totaling
(dd, 1 H, H(6´), 3J = 11.1 Hz, 3J = 4.2 Hz); 3.14 (dd, 1 H,
Hb(4), 2J = 17.0 Hz, 3J = 1.7 Hz); 3.29 (dd, 1 H, H(4´),
3J = 12.1 Hz, 3J = 2.5 Hz); 3.53, 3.62, 3.73, 3.75 (all s, 3 H each,
3
3
4 OMe); 4.46 (dd, 1 H, H(1´), J = 9.8 Hz, J = 3.1 Hz); 6.55
(dd, 1 H, H(3), 3J = 1.7 Hz, 3J = 1.4 Hz); 7.03 (m, 2 H, Ho,
Ph at C(4´)); 7.11 (m, 1 H, Hp, Ph at C(1´)); 7.16 (m, 1 H, Hp,
Ph at C(4´)); 7.17 (m, 2 H, Hm, Ph at C(1´)); 7.21 (m, 2 H, Hm,
Ph at C(4´)); 7.28 (m, 2 H, Ho, Ph at C(1´)). 13C NMR (CDCl3),
: 21.2 (Me); 31.5 (C(5´)); 42.2 (C(2´)); 46.0 (C(4)); 49.9 (C(4´));
50.3 (C(6´)); 51.1 (CO2Me at C(5)); 51.8, 51.9, 52.5, 52.6
(4 OMe); 57.8 (C(1´)); 61.1 (C(3´)); 67.7 (C(5)); 126.80 (br),
126.83 (2 Cp); 127.9 (Co, Ph at C(1´)); 128.2 (Cm, Ph at C(4´));
128.5 (Cm, Ph at C(1´)); 129.5 (br, Co, Ph at C(4´)); 136.9

1924
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 10, October, 2012
Novikov et al.
(CH(3)); 137.5 (Cipso, Ph at C(4´)); 141.7 (Cipso, Ph at C(1´));
169.4, 169.6, 170.5, 170.6 (4 COO); 172.2 (COO at C(5)).
Isomer (5R*,1´R*)ꢀ9d. Colorless dense oil. HRMS (ESI):
[M + Na]+, calculated for C32H38N2O10Na 633.2419, found
633.2412; [M + K]+, calculated for C32H38N2O10K 649.2158,
President of the Russian Federation (Program of State
Support for Leading Scientific Schools of the Russian Fedꢀ
eration, Grant NShꢀ604.2012.3).
References
1
found 649.2160. H NMR (CDCl3), : 0.77 (s, 3 H, Me); 1.88
(dd, 1 H, Ha(2´), 2J = 14.7 Hz, 3J = 1.8 Hz); 2.37 (ddd, 1 H,
Ha(5´), 2J = 13.7 Hz, 3J = 10.6 Hz, 3J = 2.5 Hz); 2.37 (dd, 1 H,
Ha(4), 2J = 17.5 Hz, 3J = 1.7 Hz); 2.63 (ddd, 1 H, Hb(5´),
1. H.ꢀU. Reissig, R. Zimmer, Chem. Rev., 2003, 103, 1151.
2. M. Yu, B. L. Pagenkopf, Tetrahedron, 2005, 61, 321.
3. F. De Simone, J. Waser, Synthesis, 2009, 20, 3353.
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haus, S. D. Sanders, J. Org. Chem., 2010, 75, 6317.
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2010, 66, 9151.
7. R. A. Novikov, E. V. Shulishov, Yu. V. Tomilov, Mendeleev
Commun., 2012, 22, 87.
8. L. A. Blanchard, J. A. Schneider, J. Org. Chem., 1986,
51, 1372.
3
3
2J = 13.7 Hz, J = 9.8 Hz, J = 4.4 Hz); 2.88 (dd, 1 H, Hb(2´),
2J = 14.7 Hz, 3J = 10.3 Hz); 2.92 (dd, 1 H, H(6´), 3J = 10.6 Hz,
3J = 4.4 Hz); 3.26 (dd, 1 H, H(4´), 3J = 9.8 Hz, J = 2.5 Hz);
3
3.51 (dd, 1 H, Hb(4), 2J = 17.5 Hz, 3J = 1.3 Hz); 3.51, 3.57, 3.73,
3.77, 3.85 (all s, 3 H each, 5 OMe); 4.84 (dd, 1 H, H(1´),
3J = 10.3 Hz, 3J = 1.8 Hz); 6.58 (dd, 1 H, H(3), 3J = 1.7 Hz,
3J = 1.3 Hz); 7.00 (m, 2 H, Ho, Ph at C(4´)); 7.11 (m, 2 H, Hp,
2 Ph); 7.18 (m, 4 H, Hm, 2 Ph); 7.41 (m, 2 H, Ho, Ph at C(1´)).
13C NMR (CDCl3), : 22.2 (Me); 31.5 (C(5´)); 42.5 (C(2´));
45.3 (C(4)); 50.6 (C(4´)); 50.5 (C(6´)); 51.75, 51.77, 51.9, 52.4,
52.6 (5 OMe); 59.1 (C(1´)); 61.4 (C(3´)); 70.5 (C(5)); 126.77,
126.80 (br, 2 Cp); 127.7 (Co, Ph at C(1´)); 127.8, 128.6 (2 Cm);
129.5 (br, Co, Ph at C(4´)); 136.4 (CH(3)); 137.4 (Cipso, Ph at
C(4´)); 145.5 (Cipso, Ph at C(1´)); 169.5, 169.6, 170.3, 170.6
(4 COO), 171.7 (COO at C(5)).
9. M. I. Uddin, A. Mimoto, K. Nakano, Y. Ichikawa, H. Kotꢀ
suki, Tetrahedron Lett., 2008, 49, 5867.
10. P. D. Pohlhaus, S. D. Sanders, A. T. Parsons, W. Li, J. S.
Johnson, J. Am. Chem. Soc., 2008, 130, 8642.
11. K. Sapeta, M. A. Kerr, Org. Lett., 2009, 11, 2081.
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This work was financially supported by the Division of
Chemistry and Materials Science of the Russian Academy
of Sciences (Program for Basic Research "Theoretical and
Experimental Studies of the Nature of Chemical Bond
and Mechanisms of the Most Important Chemical Reacꢀ
tions and Processes") and the Council on Grants at the
13. E. E. Schweizer, C. S. Kim, J. Org. Chem., 1971, 36, 4033.
Received April 10, 2012;
in revised form July 5, 2012